EP1222008A1 - Method for supercritical fluid extraction - Google Patents

Method for supercritical fluid extraction

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Publication number
EP1222008A1
EP1222008A1 EP00967975A EP00967975A EP1222008A1 EP 1222008 A1 EP1222008 A1 EP 1222008A1 EP 00967975 A EP00967975 A EP 00967975A EP 00967975 A EP00967975 A EP 00967975A EP 1222008 A1 EP1222008 A1 EP 1222008A1
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EP
European Patent Office
Prior art keywords
excipient
extraction
solvent
supercritical
extract
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EP00967975A
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German (de)
French (fr)
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EP1222008B1 (en
Inventor
Philippe Mengal
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Hitex
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Hitex
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • B01D11/02—Solvent extraction of solids
    • B01D11/0203—Solvent extraction of solids with a supercritical fluid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • B01D11/02—Solvent extraction of solids
    • B01D11/0288—Applications, solvents

Definitions

  • the invention relates to the field of methods for extracting active compounds from raw materials of natural origin, making it possible to obtain active extracts used in the formulation of cosmetic, pharmaceutical or food compositions.
  • Natural extracts obtained in particular from plants, algae, biomass or beehive products, have been used traditionally for a long time in the cosmetic, dermo-pharmaceutical, pharmaceutical or food fields. Many extraction methods are traditionally used to obtain these extracts: hydro-distillation, extraction with organic solvents, hydroglyco maceration, hxiviation, decoction, ...
  • This technology makes it possible to obtain very high quality extracts, tailor-made, according to the choice of operating parameters.
  • the solvent power of supercritical CO 2 varies as a function of the pressure and the extraction temperature. Oils rich in polyunsaturated fatty acids or fractions rich in unsaponi iable of very high quality are thus obtained by this technology.
  • the disadvantage of supercritical CO 2 extraction is the high cost linked to the low solvent power of pure CO 2 , which limits its application to a few niches.
  • a co-solvent such as ethanol, methanol or acetone can be added to the supercritical CO 2 .
  • the solvent power of supercritical CO 2 can then be increased by a factor of 10.
  • the main objective of the present invention is to propose a new method of extraction with supercntic CO 2 which does not have the above-mentioned drawback.
  • the objective of the present invention is also to propose such a simpler method than the methods of extraction by supercritical fluid of the prior art.
  • the invention which relates to a process for the extraction by supercritical fluid of one or more active compounds intended to enter into the formulation of a cosmetic, pharmaceutical or food composition containing at least one excipient, from a raw material, said method comprising the steps of; bringing said raw material containing the active compounds into contact in the presence of at least one extraction fluid in the supercritical state comprising CO 2 and at least one co-solvent, - separating said extraction fluid containing at least part active compound (s); causing the CO 2 contained in the extraction fluid to vaporize in order to obtain an extract consisting of said co-solvent and of said part of the active compound (s); - recovering said extract constituted by the co-solvent / compound (s) act ⁇ f (s) mixture; characterized in that, said co-solvent consists of said excipient.
  • the present invention is therefore based on the discovery that certain excipients compatible with cosmetic, dermo-pharmaceutical, pharmaceutical or food use can be used in admixture with supercritical CO 2 .
  • This mixture then behaves like a fluid whose solvent power can be adjusted by modifying the proportion CO 2 / exc ⁇ p ⁇ ent or by adapting the pressure and the extraction temperature.
  • the invention therefore uses the properties of superc ⁇ tic fluids or pressurized liquids, to which an excipient has been added, and having, under appropriate temperature and pressure conditions, an increased dissolving power with respect to the active agents to be extracted. , better selectivity while considerably limiting the risks of degradation of the active compounds, these being protected during the extraction process
  • the excipient-active mixture can moreover correspond to the final formulation, which constitutes an important advantage.
  • the method according to the latter comprises an additional step consisting in recycling the vaporized CO 2 , at the head of the process where it can be condensed, pumped and reheated so as to be passed back to the supercntic state .
  • the method comprises a preliminary step consisting in adding said excipient to CO 2 in the supercritical state to obtain said extraction fluid.
  • the method comprises a preliminary step consisting in adding said excipient to the liquid CO 2 under pressure and then heating the mixture obtained in order to pass the CO 2 to the supercritical state and to obtain said extraction fluid.
  • said extraction fluid has a compressed temperature between approximately 31 ° C. and approximately 100 ° C. and a compressed pressure between approximately 7.4 MPa and approximately 50 MPa.
  • excipients which can be used within the framework of the present invention can be any compound or mixture of compounds compatible with cosmetic, dermo-pharmaceutical, pharmaceutical or food use having sufficient solubility in CO 2 under pressure.
  • glycerol an excipient conventionally used in cosmetics, which is considerably insoluble in CO 2 , cannot be chosen while other compounds having a low but not zero solubility can be validly used.
  • said excipient is chosen from the group consisting of, propylene glycol, butylene glycol, polyethylene glycols of all molecular weights, monoethyl ether diethylene glycol, hexvlene glycol, polyols, glycemic fatty substances, non-glycemic fatty substances, esters, waxes, silicone oils and terpec compounds.
  • the method according to the invention is implemented with weight proportions (raw material) / (CO 2 ) / (Exc ⁇ p ⁇ ent) of (10) / (10 to 2000) / (l to 200).
  • the invention also relates to any extract obtained by a single extraction process characterized in that it consists of one or more active compounds and by at least one excipient used in the formulation of a cosmetic, pharmaceutical or food product.
  • the extracts obtained by the process which is the subject of the present invention can be used in any galemic form used in cosmetics or dermopharmaceuticals: oil in water and water in oil emulsion, shampoos and conditioners, milks, lotions, gels, ointments, hair sprays , without this list being exhaustive. They can also be used in the food and pharmaceutical fields.
  • extracts obtained by the process which is the subject of the present invention into cosmetic vectors such as liposomes, chylomicrons, macro, micro and nanoparticles, as well as macro, micro, nanocapsules. They can be absorbed on powdery organic polymers, talcs, bentonites and other mineral supports.
  • the extracts obtained by the process which is the subject of the present invention can be combined in cosmetic compositions with any other ingredient usually used in cosmetics and dermopharmaceuticals: lipids, polymers gelling agents and viscosants, surfactants and emulsifiers, hydro or liposoluble active ingredients, extracts from other raw materials.
  • compositions containing the extracts obtained by the process which is the subject of the present invention are intended for all cometic and dermopharmaceutical applications, namely in particular: care and hygiene of the skin, scalp, hair, mucous membranes, oral regions, for anti-aging treatments and sun protection, for hydration, smoothing effect or any other application.
  • the present example constitutes a comparative example between the traditional extraction with supercritical CO 2 and the extraction, according to a variant of the process which is the subject of the present invention, of ginger extract.
  • the extraction with supercritical CO 2 is carried out without co-solvent at 300 bar and 50 ° C.
  • 9 g of extract are collected by percolating 6 kg of CO 2 on 30 g of ginger previously ground and 11 g of extract are collected by percolating 12 kg of CO 2 .
  • the extract obtained pasty and "sticky" has a strong odor and flavor, characteristic of the raw material, while the residue is almost deodorized.
  • the process is then carried out under the same pressure and temperature conditions but in the presence of a co-solvent, namely propylene glycol, in mixture with CO 2 at a rate of 10 g per 1 kg of CO 2 .
  • a co-solvent namely propylene glycol
  • the product obtained thanks to the invention contains as an excipient the co-solvent and therefore has a fluid appearance, which makes it much easier to handle and formulate in a food preparation.
  • the traditional extraction with supercritical CO 2 of paprika powder is compared with the extraction according to a variant of the process which is the subject of the present invention.
  • the extract yield is very low, even for large quantities and percolated CO 2 .
  • the same color yield is achieved for 25 kg of CO 2 propylene glycol mixture for 1 kg of paprika.
  • the extract collected by decantation, including the co-solvent has a color yield of more than 200,000 UC, without the need to evaporate the co-solvent.
  • the traditional supercritical CO 2 extraction of parthenoid from Tanacetum parthenium is compared to the extraction according to a method of the process which is the subject of the present invention.
  • 14.8 g of dark green extract and resinous appearance are collected by percolating 8 kg of CO 2 on 300 g of ground drug.
  • the extract analyzed by Gas Chromatography has a 14.5% parthenoid content.
  • the raw extract In order to increase its conservation and allow the formulation of this extract in soft capsule, the raw extract must be diluted with a glyceride oil.
  • the extraction was carried out by adding to the CO 2 0.5% of a mixture of triglycerides of capric and caprylic acids. By percolating 6 kg of this mixture successively on 300 g of drug and then 1 kg of pure CO 2 , 40.5 g of weakly colored oily extract are collected. This extract titrating 5.5% (m / m) of parthenolide, it can be formulated as it is and packaged in soft capsule.
  • EXAMPLE 7 In this example, the traditional extraction with supercritical CO 2 of Calendula flowers is compared with the extraction according to a variant of the process which is the subject of the present invention.
  • Example 7 is a variant of Example 7 for which part of the water contained in the Calendula flowers is co-extracted.
  • the extract then offers the appearance of an emulsion whose properties are of interest in dermo-pharmaceutical and cosmetic preparations.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Extraction Or Liquid Replacement (AREA)
  • Cosmetics (AREA)
  • Medicines Containing Plant Substances (AREA)

Abstract

The invention relates to a method for extracting one or more active compounds from a starting material using a supercritical fluid, said compounds being for introduction into the formulation of a cosmetic, pharmaceutical or food composition containing at least one excipient. The inventive method comprises the following steps: placing said starting material containing the active compounds in the presence of at least one extraction fluid in a supercritical state and containing CO2 and at least one co-solvent; separating said extraction fluid containing at least a proportion of the active compound(s); causing the CO2 contained in the extraction fluid to vaporize in order to obtain an extract consisting of said co-solvent and said proportion of the active compound(s); recovering the extract consisting of the co-solvent/active compound mixture. The method is characterised in that said co-solvent consists of said excipient.

Description

Procédé d'extraction par fluide supercritique. Extraction process by supercritical fluid.
L'invention concerne le domaine des procédés d'extraction de composés actifs à partir de matières premières d'oπgine naturelle, permettant d'obtenir des extraits actifs entrant dans la formulation de compositions cosmétiques, pharmaceutiques ou alimentaires.The invention relates to the field of methods for extracting active compounds from raw materials of natural origin, making it possible to obtain active extracts used in the formulation of cosmetic, pharmaceutical or food compositions.
Les extraits naturels, obtenus notamment à partir de végétaux, d'algues, de biomasses ou de produits de la ruche, sont utilisés traditionnellement depuis longtemps dans le domaine cosmétique, dermo-pharmaceutique, pharmaceutique ou alimentaire. De nombreuses méthodes d'extraction sont traditionnellement mises en œuvre pour obtenir ces extraits : hydro-distillation, extraction par solvants organiques, macération hydroglycohque, hxiviation, décoction, ...Natural extracts, obtained in particular from plants, algae, biomass or beehive products, have been used traditionally for a long time in the cosmetic, dermo-pharmaceutical, pharmaceutical or food fields. Many extraction methods are traditionally used to obtain these extracts: hydro-distillation, extraction with organic solvents, hydroglyco maceration, hxiviation, decoction, ...
Ces procédés traditionnels comportent des avantages, principalement liés à la simplicité des technologies mises en œuvre, mais également des énients. A ce sujet, on peut citer les problèmes suivants : présence de solvants résiduels dans le cas d'extraction par solvant organique ; mauvaise stabilité des extraits obtenus par macération ; temps de contact très long pour les macérations rrvdroglycohques , - faible sélectiuté de l'extraction en général, entraînant une trop forte coloration des extraits. Au-delà de l'image « produit naturel », l'industrie cosmétique et dermopharmaceutique recherche aujourd'hui des produits très stables, des extraits sélectifs πches en substances actives. De plus, le coût des extraits doit être optimisé au mieux.These traditional processes have advantages, mainly related to the simplicity of the technologies used, but also énients. In this regard, the following problems may be mentioned: presence of residual solvents in the case of extraction with organic solvent; poor stability of the extracts obtained by maceration; very long contact time for rrvdroglycohques macerations, - low selection of the extraction in general, leading to too strong coloring of the extracts. Beyond the “natural product” image, the cosmetic and dermopharmaceutical industry is now looking for very stable products, with selective extracts of active substances. In addition, the cost of extracts must be optimized as much as possible.
On sait par ailleurs qu'un fluide en état supercritique, c'est-à-dire dans un état caractérisé soit par une pression et une température respectivement supéπeures à la pression et à la température en tiques dans le cas d'un corps pur, soit par un point représentatif (pression, température) situé au-delà de l'enveloppe des points critiques représentés sur un diagramme (pression, température) dans le cas d'un mélange, présente, pour de très nombreuses substances, un pouvoir solvant élevé sans commune mesure avec celui observ é dans ce même fluide à l'état de gaz comprimé. C'est la raison pour laquelle ces fluides sont utilisés dans de nombreux procédés d'extraction (solide/fluide), de fractionnement (liquide/fluide), de chromatographie analytique ou préparative, de traitement des matériaux (céramiques, polymères, ...) .We also know that a fluid in a supercritical state, that is to say in a state characterized either by a pressure and a temperature respectively greater than the pressure and the temperature in ticks in the case of a pure body, either by a representative point (pressure, temperature) located beyond the envelope critical points represented on a diagram (pressure, temperature) in the case of a mixture, presents, for very many substances, a high solvent power without common measure with that observed in this same fluid in the state of compressed gas . This is the reason why these fluids are used in many extraction processes (solid / fluid), fractionation (liquid / fluid), analytical or preparative chromatography, treatment of materials (ceramics, polymers, ... ).
À ce sujet, il est à noter que les propriétés physico-chimiques du dioxyde de carbone (CO2) ainsi que ses coordonnées critiques (pression critique : 7,4 Mpa et température critique : 31° C) en font le solvant préféré dans de nombreuses applications, surtout qu'il ne présente pas de toxicité et est disponible à un haut niveau de pureté en très grande quantité et à bas prix.In this regard, it should be noted that the physicochemical properties of carbon dioxide (CO 2 ) as well as its critical coordinates (critical pressure: 7.4 Mpa and critical temperature: 31 ° C) make it the preferred solvent in numerous applications, especially since it does not present any toxicity and is available at a high level of purity in very large quantities and at low prices.
Cette technologie permet d'obtenir des extraits de très haute qualité, sur mesure, en fonction du choix des paramètres opératoires. En effet le pouvoir solvant du CO2 supercritique varie en fonction de la pression et de la température d'extraction. Des huiles riches en acides gras polyinsaturés ou des fractions riches en insaponi iable de très grande qualité sont ainsi obtenues par cette technologie. L'inconvénient de l'extraction au CO2supercritique est le coût élevé lié au faible pouvoir solvant du CO2pur, ce qui limite son application à quelques niches. Afin d'accroître le pouvoir solvant du CO2 supercritique et donc d'augmenter la productivité du procédé, on peut ajouter au CO2 supercritique un co-solvant tel que de l'éthanol, du méthanol ou de l'acétone. Le pouvoir solvant du CO2 supercritique peut alors être augmenté d'un facteur 10. Malheureusement, le gain de productivité est compensé par la nécessité d'éliminer le solvant de l'extrait, ce qui d'une part implique une opération supplémentaire de distillation/séchage, et d'autre part engendre souvent des problèmes de stabilité. Le pπncipal objectif de la présente invention est de proposer un nouveau procédé d'extraction par CO2 supercntique ne présentant pas l'inconvénient susmentionné.This technology makes it possible to obtain very high quality extracts, tailor-made, according to the choice of operating parameters. In fact, the solvent power of supercritical CO 2 varies as a function of the pressure and the extraction temperature. Oils rich in polyunsaturated fatty acids or fractions rich in unsaponi iable of very high quality are thus obtained by this technology. The disadvantage of supercritical CO 2 extraction is the high cost linked to the low solvent power of pure CO 2 , which limits its application to a few niches. In order to increase the solvent power of supercritical CO 2 and therefore to increase the productivity of the process, a co-solvent such as ethanol, methanol or acetone can be added to the supercritical CO 2 . The solvent power of supercritical CO 2 can then be increased by a factor of 10. Unfortunately, the productivity gain is offset by the need to remove the solvent from the extract, which on the one hand involves an additional distillation operation. / drying, and on the other hand often causes stability problems. The main objective of the present invention is to propose a new method of extraction with supercntic CO 2 which does not have the above-mentioned drawback.
L'objectif de la présente invention est également de proposer un tel procédé plus simple que les procédés d'extraction par fluide supercritique de l'état de la technique.The objective of the present invention is also to propose such a simpler method than the methods of extraction by supercritical fluid of the prior art.
Ces objectifs sont atteints grâce à l'invention qui concerne un procédé d'extraction par fluide supercritique d'un ou plusieurs composés actifs destιné(s) à entrer dans la formulation d'une composition cosmétique, pharmaceutique ou alimentaire contenant au moins un excipient, à partir d'une matière première, ledit procédé comprenant les étapes consistant à ; mettre en contact ladite matière première contenant les composés actifs en présence d'au moins un fluide d'extraction à l'état supercritique comprenant du CO2 et au moins un co-solvant, - séparer ledit fluide d'extraction contenant au moins une partie du ou des composés actifs ; provoquer la vaporisation du CO2 contenu dans le fluide d'extraction pour obtenir un extrait constitué dudit co-solvant et de ladite partie du ou des composés actifs ; - récupérer ledit extrait constitué par le mélange co- solvant/composé(s) actιf(s) ; caracténsé en ce que, ledit co-solvant est constitué par ledit excipient.These objectives are achieved thanks to the invention which relates to a process for the extraction by supercritical fluid of one or more active compounds intended to enter into the formulation of a cosmetic, pharmaceutical or food composition containing at least one excipient, from a raw material, said method comprising the steps of; bringing said raw material containing the active compounds into contact in the presence of at least one extraction fluid in the supercritical state comprising CO 2 and at least one co-solvent, - separating said extraction fluid containing at least part active compound (s); causing the CO 2 contained in the extraction fluid to vaporize in order to obtain an extract consisting of said co-solvent and of said part of the active compound (s); - recovering said extract constituted by the co-solvent / compound (s) actιf (s) mixture; characterized in that, said co-solvent consists of said excipient.
La présente invention est donc basée sur la découverte que certains excipients compatibles avec un usage en cosmétique, dermo-pharmaceutique, pharmaceutique ou alimentaire peuvent êtres utilisés en mélange avec le CO2 supercritique. Ce mélange se comporte alors comme une fluide dont on peut ajuster le pouvoir solvant en modifiant la proportion CO2/excιpιent ou en adaptant la pression et la température d'extraction. L'invention utilise donc les propnétés des fluides supercπtiques ou des liquides sous pression, auxquels un excipient a été ajouté, et présentant, dans des conditions de température et de pression appropnées, un pouvoir de dissolution accru vis-à-vis des actifs à extraire, une meilleure sélectivité tout en limitant considérablement les risques de dégradation des composés actifs, ceux-ci étant protégés au cours du procédé d'extractionThe present invention is therefore based on the discovery that certain excipients compatible with cosmetic, dermo-pharmaceutical, pharmaceutical or food use can be used in admixture with supercritical CO 2 . This mixture then behaves like a fluid whose solvent power can be adjusted by modifying the proportion CO 2 / excιpιent or by adapting the pressure and the extraction temperature. The invention therefore uses the properties of supercπtic fluids or pressurized liquids, to which an excipient has been added, and having, under appropriate temperature and pressure conditions, an increased dissolving power with respect to the active agents to be extracted. , better selectivity while considerably limiting the risks of degradation of the active compounds, these being protected during the extraction process
Le mélange excipient-actif peut de plus correspondre à la formulation finale, ce qui constitue un a\ antage important.The excipient-active mixture can moreover correspond to the final formulation, which constitutes an important advantage.
Selon un aspect préférentiel de l'invention, le procédé selon celle-ci comprend une étape supplémentaire consistant à recycler le CO2 vaponsé, en tête de procédé où il peut être condensé, pompé et réchauffé pour être de nouveau passé à l'état supercntique.According to a preferred aspect of the invention, the method according to the latter comprises an additional step consisting in recycling the vaporized CO 2 , at the head of the process where it can be condensed, pumped and reheated so as to be passed back to the supercntic state .
Selon une vanante, le procédé comprend une étape préliminaire consistant à ajouter ledit excipient au CO2 à l'état supercritique pour obtenir ledit fluide d'extraction.According to a vanante, the method comprises a preliminary step consisting in adding said excipient to CO 2 in the supercritical state to obtain said extraction fluid.
Selon une autre variante, le procédé comprend une étape préliminaire consistant à ajouter ledit excipient au CO2 liquide sous pression puis à réchauffer le mélange obtenu pour faire passer le CO2 à l'état supercritique et obtenir ledit fluide d'extraction. Selon un autre aspect préférentiel de l'invention, ledit fluide d'extraction présente une température compnse entre environ 31° C et 100°C environ et une pression compnse entre environ 7,4 MPa et environ 50 MPa.According to another variant, the method comprises a preliminary step consisting in adding said excipient to the liquid CO 2 under pressure and then heating the mixture obtained in order to pass the CO 2 to the supercritical state and to obtain said extraction fluid. According to another preferred aspect of the invention, said extraction fluid has a compressed temperature between approximately 31 ° C. and approximately 100 ° C. and a compressed pressure between approximately 7.4 MPa and approximately 50 MPa.
Les excipients qui peuvent être utilisés dans le cadre de la présente invention peuvent être tout composé ou mélange de composés compatibles avec un usage cosmétique, dermo-pharmaceutique, pharmaceutique ou alimentaire présentant une solubilité suffisante dans le CO2 sous pression. Ainsi le glycérol, un excipient classiquement utilisé en cosmétique, qui est ngoureusement insoluble dans le CO2, ne peut être choisi alors que d'autres composés présentant une solubilité faible mais non nulle, peuv ent être valablement utilisés. Préférentiellement, selon que la formulation est destinée à un produit cosmétique, pharmaceutique, dermo-pharmaceutique ou alimentaire, ledit excipient est choisi dans le groupe constitué par, le propvlène glycol, le butylène glycol, les polyéthylène gl cols de tous poids moléculaires, le monoéthylether du diéthylène glycol, l'hexvlène glycol, les polyols, les corps gras glycéndiques, les corps gras non glycéndiques, les esters, les cires, les huiles sihcones et les composés terpé ques.The excipients which can be used within the framework of the present invention can be any compound or mixture of compounds compatible with cosmetic, dermo-pharmaceutical, pharmaceutical or food use having sufficient solubility in CO 2 under pressure. Thus glycerol, an excipient conventionally used in cosmetics, which is considerably insoluble in CO 2 , cannot be chosen while other compounds having a low but not zero solubility can be validly used. Preferably, depending on whether the formulation is intended for a cosmetic, pharmaceutical, dermo-pharmaceutical or food product, said excipient is chosen from the group consisting of, propylene glycol, butylene glycol, polyethylene glycols of all molecular weights, monoethyl ether diethylene glycol, hexvlene glycol, polyols, glycemic fatty substances, non-glycemic fatty substances, esters, waxes, silicone oils and terpec compounds.
Avantageusement, le procédé selon l'invention est mis en œu re avec des proportions pondérales (matière premιère)/(CO2)/(Excιpιent) de ( 10)/(10 à 2000)/(l à 200).Advantageously, the method according to the invention is implemented with weight proportions (raw material) / (CO 2 ) / (Excιpιent) of (10) / (10 to 2000) / (l to 200).
L'invention concerne également tout extrait obtenu grâce à un seul procédé d'extraction caracténsé en ce qu'il est constitué par un ou plusieurs composés actifs et par au moins un excipient entrant dans la formulation d'un produit cosmétique, pharmaceutique ou alimentaire. Les extraits obtenus par le procédé objet de la présente invention peuvent être utilisés dans toute forme galémque employée en cosmétique ou dermopharmaceutique : émulsion huile dans eau et eau dans huile, shampooings et après-shampooings, laits, lotions, gels, pommades, laques pour cheveux, sans que cette liste soit exhaustive. Ils peuvent également être utilisés dans le domaine alimentaire et pharmaceutique.The invention also relates to any extract obtained by a single extraction process characterized in that it consists of one or more active compounds and by at least one excipient used in the formulation of a cosmetic, pharmaceutical or food product. The extracts obtained by the process which is the subject of the present invention can be used in any galemic form used in cosmetics or dermopharmaceuticals: oil in water and water in oil emulsion, shampoos and conditioners, milks, lotions, gels, ointments, hair sprays , without this list being exhaustive. They can also be used in the food and pharmaceutical fields.
Il est possible d'incorporer les extraits obtenus par le procédé objet de la présente invention dans des vecteurs cosmétiques tels que les liposomes, les chylomicrons, les macro, micro et nanoparticules, ainsi que les macro, micro, nanocapsules. On peut les absorber sur des polymères organiques poudreux, des talcs, bentonites et autres supports minéraux.It is possible to incorporate the extracts obtained by the process which is the subject of the present invention into cosmetic vectors such as liposomes, chylomicrons, macro, micro and nanoparticles, as well as macro, micro, nanocapsules. They can be absorbed on powdery organic polymers, talcs, bentonites and other mineral supports.
Les extraits obtenus par le procédé objet de la présente invention peuvent être combinés dans des compositions cosmétiques avec tout autre ingrédient habituellement utilisé en cosmétique et dermopharmaceutique : lipides, polymères gélifiants et viscosants, tensioactifs et émulsifiants, principes actif hydro ou liposolubles, extraits d'autres matières premières.The extracts obtained by the process which is the subject of the present invention can be combined in cosmetic compositions with any other ingredient usually used in cosmetics and dermopharmaceuticals: lipids, polymers gelling agents and viscosants, surfactants and emulsifiers, hydro or liposoluble active ingredients, extracts from other raw materials.
Les compositions cosmétiques ou dermopharmaceutiques contenant les extraits obtenus par le procédé objet de la présente invention, sont destinées à toute les applications cométiques et dermopharmaceutiques, à savoir notamment : soin et hygiène de la peau, du cuir chevelu, des cheveux, des muqueuses, des régions bucco-dentaires, pour les traitements anti-vieillissement et la protection solaire, pour l'hydratation, l'effet lissage ou toute autre applications.The cosmetic or dermopharmaceutical compositions containing the extracts obtained by the process which is the subject of the present invention are intended for all cometic and dermopharmaceutical applications, namely in particular: care and hygiene of the skin, scalp, hair, mucous membranes, oral regions, for anti-aging treatments and sun protection, for hydration, smoothing effect or any other application.
L'invention, ainsi que les avantages qu'elle présente seront plus facilement compris grâce aux exemples de réalisation de celle-ci exposée ci-après.The invention, as well as the advantages which it presents, will be more easily understood thanks to the exemplary embodiments thereof set out below.
EXEMPLE 1EXAMPLE 1
Le présent exemple constitue un exemple comparatif entre l'extraction traditionnelle au CO2 supercritique et l'extraction, selon une variante du procédé objet de la présente invention, d'extrait de gingembre.The present example constitutes a comparative example between the traditional extraction with supercritical CO 2 and the extraction, according to a variant of the process which is the subject of the present invention, of ginger extract.
Selon le procédé classique, l' extraction au CO2 supercritique est effectuée sans co-solvant à 300 bar et 50°C. 9 g d'extrait sont collectés en faisant percoler 6 kg de CO2 sur 30 g de gingembre préalablement broyés et 11 g d'extrait sont collectés en faisant percoler 12 kg de CO2. Dans ces conditions, l'extrait obtenu pâteux et " collant" présente une odeur et une flaveur puissante, caractéristique de la matière première, tandis que le résidu est presque désodorisé.According to the conventional process, the extraction with supercritical CO 2 is carried out without co-solvent at 300 bar and 50 ° C. 9 g of extract are collected by percolating 6 kg of CO 2 on 30 g of ginger previously ground and 11 g of extract are collected by percolating 12 kg of CO 2 . Under these conditions, the extract obtained pasty and "sticky" has a strong odor and flavor, characteristic of the raw material, while the residue is almost deodorized.
Selon l'invention, le procédé est ensuite mis en oeuvre dans les mêmes conditions de pression et de température mais en présence d'un co-solvant, à savoir du propylène glycol, en mélange avec le CO2 à raison de 10 g pour 1 kg de CO2.According to the invention, the process is then carried out under the same pressure and temperature conditions but in the presence of a co-solvent, namely propylene glycol, in mixture with CO 2 at a rate of 10 g per 1 kg of CO 2 .
L'utilisation d'un co-solvant permet d'accroître la performance du procédé d'extraction.The use of a co-solvent makes it possible to increase the performance of the extraction process.
Plus précisément, grâce à l'invention, 5 kg de mélange CO2 propylène glycol sont suffisants pour obtenir un produit constitué d'extrait de gingembre et de propylène glycol présentant un pouvoir aromatique (par exemple selon l'indice Scov ille tel que défini dans l'ouv rage "Epices et aromates" -éditions Lavoisier - 1992) équivalent à celui de l'extrait obtenu sans co-solvant en utilisant 12 kg de CO2. De plus, le produit obtenu grâce à l'inv ention, contient comme excipient le co-solv ant et présente de ce fait un aspect fluide, ce qui le rend beaucoup plus aisé à manipuler et à formuler dans une préparation alimentaire.More specifically, thanks to the invention, 5 kg of CO 2 propylene glycol mixture are sufficient to obtain a product consisting of ginger extract and propylene glycol having an aromatic power (for example according to the index Scov ille as defined in the book "Spices and herbs" (Lavoisier editions - 1992) equivalent to that of the extract obtained without co-solvent using 12 kg of CO 2 . In addition, the product obtained thanks to the invention, contains as an excipient the co-solvent and therefore has a fluid appearance, which makes it much easier to handle and formulate in a food preparation.
EXEMPLE 2EXAMPLE 2
Dans cet exemple, l'extraction traditionnelle au CO2 supercritique du poivre blanc est comparée à l'extraction selon une ariante du procédé objet de la présente invention.In this example, the traditional extraction with supercritical CO 2 of white pepper is compared with the extraction according to a method of the process which is the subject of the present invention.
En extraction au CO2 supercntique sans co-solvant à 300 bar et 40°C, 10 g d'extrait sont collectés en faisant percoler 20 kg de CO2 sur 500 g de poivre blanc concassé. Dans ces conditions, l'extrait obtenu d'aspect résineux présente une flaveur puissante et piquante, caracténstique de la matière première. Dans les mêmes conditions de pression et de température, l'ajout de propylène glycol à raison de 10 g pour 1 kg de CO2 permet d'accroître la performance du procédé. Dans ces conditions, 10 kg de mélange CO2 propylène glycol sont suffisants pour obtenir le même pouvoir d'aromatisation, tandis que l'extrait obtenu, d'aspect fluide, est aisé à manipuler et à formuler dans une préparation alimentaire.In extraction with supercntic CO 2 without co-solvent at 300 bar and 40 ° C, 10 g of extract are collected by percolating 20 kg of CO 2 on 500 g of crushed white pepper. Under these conditions, the extract obtained with a resinous appearance has a powerful and pungent flavor, characteristic of the raw material. Under the same pressure and temperature conditions, the addition of propylene glycol at the rate of 10 g per 1 kg of CO 2 makes it possible to increase the performance of the process. Under these conditions, 10 kg of CO 2 propylene glycol mixture are sufficient to obtain the same flavoring power, while the extract obtained, of fluid appearance, is easy to handle and to formulate in a food preparation.
EXEMPLE 3EXAMPLE 3
Cet exemple est une vanante de l'exemple 2 pour laquelle le propylène glycol est remplacé par de l'huile d'arachide ajoutée à 5 g par kg de CO2. L'extrait obtenu, d'aspect huileux est particulièrement adapté à la formulation de préparation alimentaire en présence d'autres corps gras. EXEMPLE 4This example is a summary of Example 2 for which the propylene glycol is replaced by peanut oil added to 5 g per kg of CO 2 . The extract obtained, with an oily appearance, is particularly suitable for the formulation of food preparation in the presence of other fatty substances. EXAMPLE 4
Dans cet exemple, l'extraction traditionnelle au CO2 supercritique de poudre de paprika est comparée à l'extraction selon une variante du procédé objet de la présente invention . En extraction au CO2 supercritique sans co-solvant à 300 bar et 60°C, le rendement en extrait est très faible, même pour des quantités importantes et CO2 percolé.In this example, the traditional extraction with supercritical CO 2 of paprika powder is compared with the extraction according to a variant of the process which is the subject of the present invention. In extraction with supercritical CO 2 without co-solvent at 300 bar and 60 ° C, the extract yield is very low, even for large quantities and percolated CO 2 .
En ajoutant au CO2, 5% d'alcool éthvhque pour en accroître le pouvoir solvant, 30 kg de mélange CO2 + alcool sont nécessaires pour obtenir un "rendement couleur" de 50 g d'oléorésme à 110 000 UC (UC : Unités Couleur selon la norme American Spice Trade Association Analytical Methods (1986) /ASTAA New-york Method N°20.0 ), pour 1 kg de papnka après avoir évaporé l'alcool.By adding to the CO 2 , 5% of ethyl alcohol to increase the solvent power, 30 kg of CO 2 + alcohol mixture are necessary to obtain a "color yield" of 50 g of oleoresism at 110,000 UC (UC: Units Color according to the American Spice Trade Association Analytical Methods (1986) / ASTAA New-York Method No. 20.0) standard, for 1 kg of papnka after evaporating the alcohol.
En mettant en oeuvre le procédé objet de la présente invention en ajoutant 5 g de propylène glycol par kg de CO2, le même rendement couleur est atteint pour 25 kg de mélange CO2 propylène glycol pour 1 kg de paprika. L'extrait collecté par décantation, incluant le co-solvant, présente un rendement couleur de plus de 200 000 UC et ce, sans qu'il soit nécessaire de procéder à l'évaporation de co-solvant.By implementing the process which is the subject of the present invention by adding 5 g of propylene glycol per kg of CO 2 , the same color yield is achieved for 25 kg of CO 2 propylene glycol mixture for 1 kg of paprika. The extract collected by decantation, including the co-solvent, has a color yield of more than 200,000 UC, without the need to evaporate the co-solvent.
EXEMPLE 5EXAMPLE 5
Dans cet exemple, l'extraction traditionnelle au CO2 supercritique de parthénohde de Tanacetum parthenium est comparée à l'extraction selon une vanante du procédé objet de la présente invention. En extraction au CO2 supercntique sans co-solvant à 300 bar et 40°C, 14,8 g d'extrait vert foncé et d'aspect résineux sont collectés en faisant percoler 8 kg de CO2 sur 300 g de drogue broyée. L'extrait analysé en Chromatographie en Phase Gazeuse titre 14,5 % en parthénohde. Le rendement en parthénohde est donc de 14,8 x 0,145/300 = 0,715%. Le lot de plante utilisé titrant 0,8% en parthénohde, on peut considérer que 90% a été extrait. Afin d'accroître sa conservation et de permettre la formulation de cet extrait en capsule molle, l'extrait brut doit être dilué avec une huile glycéridique.In this example, the traditional supercritical CO 2 extraction of parthenoid from Tanacetum parthenium is compared to the extraction according to a method of the process which is the subject of the present invention. In extraction with supercntic CO 2 without co-solvent at 300 bar and 40 ° C, 14.8 g of dark green extract and resinous appearance are collected by percolating 8 kg of CO 2 on 300 g of ground drug. The extract analyzed by Gas Chromatography has a 14.5% parthenoid content. The parthenoid yield is therefore 14.8 x 0.145 / 300 = 0.715%. The batch of plant used titrating 0.8% in parthenohde, we can consider that 90% was extracted. In order to increase its conservation and allow the formulation of this extract in soft capsule, the raw extract must be diluted with a glyceride oil.
Dans les mêmes conditions de pression et de température, l'extraction a été réalisée en ajoutant au CO2 0,5% d'un mélange de triglycérides d'acides caprique et caprylique. En percolant successivement 6 kg de ce mélange sur 300 g de drogue puis 1 kg de CO2 pur, 40,5 g d'extrait huileux faiblement coloré sont collectés. Cet extrait titrant 5,5 % (m/m) en parthénolide, il peut être formulé en l'état et conditionné en capsule molle.Under the same pressure and temperature conditions, the extraction was carried out by adding to the CO 2 0.5% of a mixture of triglycerides of capric and caprylic acids. By percolating 6 kg of this mixture successively on 300 g of drug and then 1 kg of pure CO 2 , 40.5 g of weakly colored oily extract are collected. This extract titrating 5.5% (m / m) of parthenolide, it can be formulated as it is and packaged in soft capsule.
EXEMPLE 6EXAMPLE 6
Dans cet exemple, l'extraction traditionnelle au CO2 supercritique de kawa lactones de kawa-kawa (Piper methysticum) est comparée à l'extraction selon une variante du procédé objet de la présente invention.In this example, the traditional extraction with supercritical CO 2 of kawa lactones of kawa-kawa (Piper methysticum) is compared with the extraction according to a variant of the process which is the subject of the present invention.
En extraction au CO2 supercritique sans co-solvant à 300 bar et 40°C, 21,5 g d'extrait jaune orangé visqueux sont collectés en faisant percoler 10 kg de CO2 sur 350 g de plante broyée. L'extrait analysé par HPLC titre 85% en kawa lactones total. Cet extrait doit ensuite être standardisé à 30% de kawa lactones en le mélangeant avec un excipient.In extraction with supercritical CO 2 without co-solvent at 300 bar and 40 ° C, 21.5 g of viscous orange-yellow extract are collected by percolating 10 kg of CO2 on 350 g of ground plant. The extract analyzed by HPLC titers 85% in total kawa lactones. This extract must then be standardized to 30% kawa lactones by mixing it with an excipient.
En réalisant l'extraction selon le procédé objet de la présente invention en ajoutant au CO2 2% (m/m) de triglycérides d'acide caprique et caprylique, l'extrait collecté jaune vif d'aspect huileux est standardisé à 30% de kawa lactones en limitant la perte de principe actif par dégradation.By carrying out the extraction according to the process which is the subject of the present invention by adding 2% (m / m) of capric and caprylic acid triglycerides to the CO2, the bright yellow collected extract of oily appearance is standardized to 30% kawa. lactones by limiting the loss of active ingredient by degradation.
EXEMPLE 7 Dans cet exemple, l'extraction traditionnelle au CO2 supercritique de fleurs de Calendula est comparée à l'extraction selon une variante du procédé objet de la présente invention.EXAMPLE 7 In this example, the traditional extraction with supercritical CO 2 of Calendula flowers is compared with the extraction according to a variant of the process which is the subject of the present invention.
Par extraction au CO2 supercritique auquel sont ajoutés 3% d'un mélange de triglycérides d'acides caprique et caprylique, on observe une cinétique d'extraction de la lutéine utilisée comme traceur deux fois plus rapide que par extraction au CO2 sans excipient. De plus, l'extrait obtenu par le procédé objet de la présente invention est beaucoup plus facile à employer dans des préparations dermo- pharmaceutiques et cosmétiques.By supercritical CO2 extraction to which 3% of a mixture of capric and caprylic acid triglycerides are added, kinetics are observed. of lutein extraction used as a tracer twice as fast as by extraction with CO 2 without excipient. In addition, the extract obtained by the process which is the subject of the present invention is much easier to use in dermopharmaceutical and cosmetic preparations.
EXEMPLE 8EXAMPLE 8
Cet exemple est une variante de i 'exemple 7 pour lequel une partie de l'eau contenue dans les fleurs de Calendula est co-extraite. L'extrait offre alors l'aspect d'une émulsion dont les propriétés présentent un intérêt dans les préparations dermo-pharmaceutiques et cosmétiques.This example is a variant of Example 7 for which part of the water contained in the Calendula flowers is co-extracted. The extract then offers the appearance of an emulsion whose properties are of interest in dermo-pharmaceutical and cosmetic preparations.
Les modes de réalisation de l'invention ici décrits n'ont nullement pour objet de réduire la portée de l'invention. Il pourra donc y être apporté de nombreuses modifications sans sortir du cadre de celles-ci. The embodiments of the invention described here are in no way intended to reduce the scope of the invention. Many modifications can therefore be made to it without going beyond the scope of these.

Claims

REVENDICATIONS
1. Procédé d'extraction par fluide supercritique d'un ou plusieurs composés actifs destiné(s) à entrer dans la formulation d'une composition cosmétique, pharmaceutique ou alimentaire contenant au moins un excipient, à partir d'une matière première, ledit procédé comprenant les étapes consistant à ; mettre en contact ladite matière première contenant les composés actifs en présence d'au moins un fluide d'extraction à l'état supercritique comprenant du CO2 et au moins un co-solvant, séparer ledit fluide d'extraction contenant au moins une partie du ou des composés actifs ; provoquer la vaporisation du CO2 contenu dans le fluide d'extraction pour obtenir un extrait constitué dudit co-solvant et de ladite partie du ou des composés actifs ; récupérer ledit extrait constitué par le mélange co- solvant/composé(s) actif(s) ; caractérisé en ce que, ledit co-solvant est constitué par ledit excipient. 1. Process for the extraction by supercritical fluid of one or more active compounds intended to enter into the formulation of a cosmetic, pharmaceutical or food composition containing at least one excipient, from a raw material, said process comprising the steps of; contacting said raw material containing the active compounds in the presence of at least one extraction fluid in the supercritical state comprising CO 2 and at least one co-solvent, separating said extraction fluid containing at least part of the or active compounds; causing the CO 2 contained in the extraction fluid to vaporize in order to obtain an extract consisting of said co-solvent and of said part of the active compound (s); recovering said extract consisting of the co-solvent / active compound (s) mixture; characterized in that, said co-solvent consists of said excipient.
2. Procédé selon la revendication 1 caractérisé en ce qu'il comprend une étape consistant à recycler le CO2 vaporisé.2. Method according to claim 1 characterized in that it comprises a step consisting in recycling the vaporized CO 2 .
3. Procédé selon l'une quelconque des revendications 1 ou 2 caractérisé en ce qu'il comprend une étape préliminaire consistant à ajouter ledit excipient au CO2 à l'état supercritique pour obtenir ledit fluide d'extraction. 3. Method according to any one of claims 1 or 2 characterized in that it comprises a preliminary step consisting in adding said excipient to CO 2 in the supercritical state to obtain said extraction fluid.
4. Procédé selon l'une quelconque des revendications 1 ou 2 caractérisé en ce qu'il comprend une étape préliminaire consistant à ajouter ledit excipient au CO2 liquide sous pression puis à réchauffer le mélange obtenu pour faire passer le CO2 à l'état supercritique et obtenir ledit fluide d'extraction. 4. Method according to any one of claims 1 or 2 characterized in that it comprises a preliminary step consisting of adding said excipient to the liquid CO 2 under pressure and then heating the mixture obtained to bring the CO 2 to the state supercritical and obtain said extraction fluid.
5. Procédé selon l'une quelconque des revendications 1 à 4 caractérisé en ce que ledit fluide d'extraction présente une température comprise entre environ 31°C et 100°C environ et une pression comprise entre environ 7,4 MPa et environ 50 MPa. 5. Method according to any one of claims 1 to 4 characterized in that said extraction fluid has a temperature between about 31 ° C and about 100 ° C and a pressure between about 7.4 MPa and about 50 MPa .
6. Procédé selon l'une quelconque des revendications 1 à 5 caractérisé en ce que ledit excipient est choisi dans le groupe constitué par ledit excipient est choisi dans le groupe constitué par, le propylène glycol, le butylène glycol, les polyéthylène glycols de tous poids moléculaires, le monoéthylether du diéthylène glycol, l'hexylène glycol, les polyols, les corps gras glvcéridiques, les corps gras non glvcéridiques, les esters, les cires, les huiles silicones et les composés terpéniques.6. Method according to any one of claims 1 to 5 characterized in that said excipient is chosen from the group consisting of said excipient is chosen from the group consisting of, propylene glycol, butylene glycol, polyethylene glycols of all weights molecular, monoethyl ether of diethylene glycol, hexylene glycol, polyols, fatty fatty acids, non-fatty fatty substances, esters, waxes, silicone oils and terpene compounds.
7. Procédé selon l'une quelconque des revendications 1 à 6 caractérisé en ce qu'il est mis en œuvre avec des proportions pondérales (matière première)/ (CO2)/(excipient) de (10)/(10 à 2000)/(l à 200). 7. Method according to any one of claims 1 to 6 characterized in that it is implemented with weight proportions (raw material) / (CO 2 ) / (excipient) of (10) / (10 to 2000) / (l to 200).
8. Extrait obtenu grâce au procédé d'extraction selon l'une quelconque des revendications 1 à 7 caractérisé en ce qu'il est constitué par un ou plusieurs composés actifs et par au moins un excipient entrant dans la formulation d'un composé cosmétique, pharmaceutique ou alimentaire. 8. Extract obtained by the extraction process according to any one of claims 1 to 7, characterized in that it consists of one or more active compounds and by at least one excipient used in the formulation of a cosmetic compound, pharmaceutical or food.
EP00967975A 1999-10-19 2000-10-06 Method for supercritical fluid extraction Expired - Lifetime EP1222008B1 (en)

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EA012049B1 (en) * 2003-11-19 2009-08-28 Скф Технолоджис А/С A method and process for controlling the temperature, pressure and density profiles in dense fluid processes
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FR2901125B1 (en) * 2006-05-22 2009-02-13 Oreal PREPARATION OF A FORMULATION FROM A PRESSURIZED FLUID, A COSMETIC AGENT AND A HYDROXYL HYDROTROPE, A PROCESSING METHOD EMPLOYING THE SAME
FR2901130B1 (en) * 2006-05-22 2008-07-18 Oreal PREPARATION OF FORMULATION FROM PRESSURIZED FLUID OF COSMETIC AGENT AND CATIONIC HYDROTROPE PROCESSING METHOD EMPLOYING THE SAME
FR2901131B1 (en) * 2006-05-22 2008-07-18 Oreal PREPARATION OF FORMULATION FROM PRESSURIZED FLUID, COSMETIC AGENT AND ANIONIC HYDROTROPY, PROCESSING PROCESS EMPLOYING THE SAME
US20090226549A1 (en) 2008-03-06 2009-09-10 Kenneth John Hughes Herbal extracts and flavor systems for oral products and methods of making the same
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